Quartz crystal microbalance and spectroscopy measurements for acid doping in polyaniline films

Abstract

We investigated the doping of thin polyaniline (PANI) films, prepared by the chemical oxidation of aniline, with different acids. The initial step in the investigation is the preparation of PANI films from aqueous hydrochloric acid solution. This is followed by dedoping with ammonia to obtain a PANI base, which is subsequently doped with strong acids (e.g. hydrochloric, sulfuric, phosphoric and trichloroacetic acids) and with a weak acid (acetic acid). The dopant weight fraction (w), which is connected with the gain of mass during the doping of PANI, was determined in situ using a quartz crystal microbalance (QCM). The behavior of PANI upon doping with different anions derived from strong acids indicates that both proton and the anion uptake into the polymer chains occur sharply, rapidly, completely, and reversibly. However the uptake in the case in acetic acid is characterized by slow diffusion. The doping was studied at different concentrations of acetic acid. A second cycle of dedoping–redoping was also performed. The kinetics of the doping reaction is dominated by Fickian diffusion kinetics. The diffusion coefficients (D) of the dopant ions into the PANI chains were determined using the QCM and by UV–Vis absorption spectroscopy in the range of (0.076–1.64)× 10^?15 cm² s^?1. It was found that D in the second cycle of doping is larger than that evaluated from the first cycle of doping for high concentrations of acetic acid. D for the diffusion and for the dopant ion expulsion from the PANI chains was also determined during the redoping process. It was found that D for acetic acid ions in the doping process is larger than that calculated for the dedoping process.     

A Multifunctional Organic Electrolyte Additive for Aqueous Zinc Ion Batteries Based on Polyaniline Cathode

The practical applications of aqueous zinc ion batteries are hindered by the formation of dendrites on the anode, the narrow electrochemical window of electrolyte, and the instability of the cathode. To address all these challenges simultaneously, a multi-functional electrolyte additive of 1-phenylethylamine hydrochloride (PEA) is developed for aqueous zinc ion batteries based on polyaniline (PANI) cathode. Experiments and theoretical calculations confirm that the PEA additive can regulate the solvation sheath of Zn²⁺ and form a protective layer on the surface of the Zn metal anode. This broadens the electrochemical stability window of the aqueous electrolyte and enables uniform deposition of Zn. On the cathode side, the Cl⁻ anions from PEA enter the PANI chain during charge and release fewer water molecules surrounding the oxidized PANI, thus suppressing harmful side reactions. When used in a Zn||PANI battery, this cathode/anode compatible electrolyte exhibits excellent rate performance and long cycle life, making it highly attractive for practical applications.     

Preparation of NiCoFe-hydroxide/polyaniline composite for enhanced-performance supercapacitors

Ternary NiCoFe layer hydroxides with different Ni/Co/Fe molar ratios were prepared using simple urea method. By finely tuning Ni/Co/Fe molar ratio, the optimized hydroxide (LDH_2.0), a Ni/Co/Fe molar ratio of 2.0/1.0/1.0, provided high specific capacitance (408 F g⁻¹ at 2.0 A g⁻¹) and good stability (90.9% retention over 1000 cycles) due to maximum crystallinity (91.35% crystallinity) and specific surface area (160 m² g⁻¹). In order to further improve the electrochemical performances, the LDH_2.0 was made into a composite (LDH/PANI) with polyaniline (PANI) via in situ polymerization of aniline monomer. The LDH/PANI composite had a much higher specific capacitance (717 F g⁻¹ at 2.0 A g⁻¹) compared with the LDH_2.0, and a significant improvement of cycleability (84.7% retention over 1000 cycles). The results indicated that the LDH/PANI had a synergistic effect of both components due to the complementary properties, which guaranteed a good electric contact and consequently increased the specific capacitance. These provided a new approach for designing organic-inorganic composite materials with potential application in supercapacitors.     

Enabling Superior Sodium Capture for Efficient Water Desalination by a Tubular Polyaniline Decorated with Prussian Blue Nanocrystals

The application of electrochemical energy storage materials to capacitive deionization (CDI), a low-cost and energy-efficient technology for brackish water desalination, has recently been proven effective in solving problems of traditional CDI electrodes, i.e., low desalination capacity and incompatibility in high salinity water. However, Faradaic electrode materials suffer from slow salt removal rate and short lifetime, which restrict their practical usage. Herein, a simple strategy is demonstrated for a novel tubular-structured electrode, i.e., polyaniline (PANI)-tube-decorated with Prussian blue (PB) nanocrystals (PB/PANI composite). This composite successfully combines characteristics of two traditional Faradaic materials, and achieves high performance for CDI. Benefiting from unique structure and rationally designed composition, the obtained PB/PANI exhibits superior performance with a large desalination capacity (133.3 mg g⁻¹ at 100 mA g⁻¹), and ultrahigh salt-removal rate (0.49 mg g⁻¹ s⁻¹ at 2 A g⁻¹). The synergistic effect, interfacial enhancement, and desalination mechanism of PB/PANI are also revealed through in situ characterization and theoretical calculations. Particularly, a concept for recovery of the energy applied to CDI process is demonstrated. This work provides a facile strategy for design of PB-based composites, which motivates the development of advanced materials toward high-performance CDI applications.     

Solution processible and conductive polyaniline via protonation with 4,4-bis(4-hydroxy phenyl)-valeric acid: Preparation and characterization

It is demonstrated that polyaniline salt, obtained by simple protonation of its base form with 4,4-bis(4-hydroxy phenyl)-valeric acid (HPVA), combines solution processibility with electrical conductivity. The solution of PANI–HPVA in DMF and m-cresol mixture has been characterized by UV–vis spectroscopy, exhibiting spectral features characteristic of the protonated state. Precipitation of dissolved PANI–HPVA with chloroform, leads to powder of spherical morphology with an average particle size of 400 nm which is amorphous by X-ray. Their conductivity is ca. 10^− 3 S/cm (measured for pressed pellets). Thermogravimetric investigations indicate good thermal stability of this novel form of polyaniline, however some weight loss is observed below 200 °C, associated with the removal of minute amounts of solvent entrapped within PANI–HPVA grains in the precipitation process. PANI–HPVA has film forming properties and free standing films (conductivity ca. 10^− 4 S/cm) can be obtained by dissolving the powders in DMF, followed by casting.     

Structural and magnetic properties of nanocomposites based on nanostructured polyaniline and titania nanotubes

Nanocomposites consisting of self-assembled polyaniline (PANI) nanostructures and titania nanotubes (TiO₂-NT) were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous dispersion of TiO₂-NT (outer diameter ~10 nm), without added acid. The influence of initial mole ratio of aniline to TiO₂ (80, 20, and 5) on the morphology, electrical conductivity, molecular structure, crystallinity, and magnetic properties of synthesized PANI/TiO₂ nanocomposites was studied. Transmission electron microscopy, Raman spectroscopy, and X-ray powder diffraction proved that the shape and structure of TiO₂-NT in the final nanocomposites were preserved. The shape of PANI nanostructures formed in the nanocomposites was influenced by the initial aniline/TiO₂-NT mole ratio. Nanotubes and nanorods are predominant PANI nanostructures in the nanocomposite prepared with the highest aniline/TiO₂ mol ratio of 80. The decrease of aniline/TiO₂ molar ratio induced more pronounced formation of nanorod network. The electrical conductivity of PANI/TiO₂ nanocomposites was in the range (1.3–2.4) × 10^?3 S cm^?1. The nanocomposites exhibit weak ferromagnetic behavior. Approximately order of magnitude lower values of coercive field and remanent magnetization were obtained for nanocomposite samples in comparison to pure PANI.     

Turn-on and near-infrared fluorescent sensing for 2,4,6-trinitrotoluene based on hybrid (gold nanorod)-(quantum dots) assembly

In this study, we design a FRET system consisting of gold nanorod (AuNR) and quantum dots (QDs) for turn-on fluorescent sensing of 2,4,6-trinitrotoluene (TNT) in near-infrared region. The amine-terminated AuNR and carboxyl-terminated QDs first form a compact hybrid assembly through amine-carboxyl attractive interaction, which leads to a high-efficiency (>92%) FRET from QDs to AuNRs and an almost complete emission quenching. Next, added TNT molecules break the preformed assembly because they can replace the QDs around AuNRs, based on the specific reaction of forming Meisenheimer complexes between TNT and primary amines. Thus, the FRET is switched off, and a more than 10 times fluorescent enhancement is obtained. The fluorescence turn-on is immediate, and the limit of detection for TNT is as low as 0.1 nM. Importantly, TNT can be well distinguished from its analogues due to their electron deficiency difference. The developed method is successfully applied to TNT sensing in real environmental samples.     

聚苯胺复合膜的制备及性质

用溶液共混法制备聚苯胺与聚酰胺的复合膜,并研究了复合膜的性能。将化学氧化法制备的本征态聚苯胺用樟脑磺酸(PANI—CSA)掺杂后,与基体聚合物聚酰胺-66,聚酰胺-1010或聚酰胺-11同时溶解在间甲酚溶剂中,干法浇膜,制得的复合膜的电导率处于10^-6S／m～10^2S／m范围,导电阈值2％。DSC法对复合膜热性能和结晶性能进行了研究。采用三种不同pH值的溶液对复合膜进行了处理,对其导电性能的变化进行了测试。     

Highly conductive graphene oxide/polyaniline hybrid polymer nanocomposites with simultaneously improved mechanical properties

Graphene oxide (GO) was added to a polymer composites system consisting of surfactant-wrapped/doped polyaniline (PANI) and divinylbenzene (DVB). The nanocomposites were fabricated by a simple blending, ultrasonic dispersion and curing process. The new composites show higher conductivity (0.02–9.8 S/cm) than the other reported polymer system filled with PANI (10⁻⁹–10⁻¹ S/cm). With only 0.45 wt% loading of GO, at least 29% enhancement in electric conductivity and 29.8% increase in bending modulus of the composites were gained. Besides, thermal stability of the composites was also improved. UV–Vis spectroscopy, X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM) revealed that addition of GO improves the dispersion of PANI in the polymer composite, which is the key to realize high conductivity.     

Spray synthesis of rapid recovery ZnO/polyaniline film ammonia sensor at room temperature

As an excellent room temperature sensing material, polyaniline (PANI) needs to be further investigated in the field of high sensitivity and sustainable gas sensors due to its long recovery time and difficulty to complete recovery. The ZnO/PANI film with p‒n heterogeneous energy levels have successfully prepared by spraying ZnO nanorod synthesized by hydrothermal method on the PANI film rapidly synthesized at the gas‒liquid interface. The presence of p‒n heterogeneous energy levels enables the ZnO/PANI film to detect 0.1‒100 ppm (1 ppm = 10⁻⁶) NH₃ at room temperature with the response value to 100 ppm NH₃ doubled (12.96) and the recovery time shortened to 1/5 (31.2 s). The ability of high response and fast recovery makes the ZnO/PANI film to be able to detect NH₃ at room temperature continuously. It provides a new idea for PANI to prepare sustainable room temperature sensor and promotes the development of room temperature sensor in public safety.     

Impact of interfacial interactions on optical and ammonia sensing in zinc oxide/polyaniline structures

Zinc oxide/polyaniline (ZnO/PANI) hybrid structures have been investigated for their optical and gas sensing properties. ZnO nanoparticles, prepared by the sol–gel method, pressed in the form of pellets were used for gas sensing. The hybrid ZnO/PANI structure was obtained by the addition of PANI on the surface of ZnO. The UV–Vis absorption of the modified pellets show band edge at 363 nm corresponding to ZnO, while a change in the absorption peaks for PANI was observed. The possible interaction between Zn^2?+? of ZnO and NH-group of PANI was confirmed using Raman spectroscopy studies. The results reveal that the hybrid structures exhibit much higher sensitivity to NH $_{{3}}$ gas at room temperature than blank ZnO, which is sensitive to NH₃ gas at higher temperature. This enhancement has been attributed to the creation of active sites on the ZnO surface due to the presence of PANI.     

Free‐Standing,Multilayered Graphene/Polyaniline‐Glue/Graphene Nanostructures for Flexible,Solid‐State Electrochemical Capacitor Application

Graphene/polyaniline multilayered nanostructures (GPMNs) are prepared using a straightforward process through which graphite is physically exfoliated with quaternary polyaniline (PANI)‐glue. This is only accomplished by sonication of the graphite flakes in an organic solvent to form continuous films with PANI. During the sonication, the conductive PANI‐glue is spontaneously intercalated between the graphene sheet layers without deterioration of the sp² hybridized bonding structure. The resultant free‐standing, flexible films are composed of a network of overlapping graphene sheets and are shown to have a long‐range structure. The effects of different PANI content ratios and different interfacial energies (depending on the dispersion solvent) on the morphology and properties of the resulting GPMN are examined. It is found that GPMNs dispersed in water have a maximum specific capacitance of 390 F g⁻¹ in a three‐electrode configuration. Importantly, the unique structural design of GPMNs enables their use as electrode materials for the fabrication of flexible, solid‐state electrochemical capacitors, which show an enhanced performance compared to graphene‐only devices. They exhibit a high specific capacitance of 200 F g⁻¹, a cycling stability with capacitance retention of 82% after 5000 charge/discharge cycles, and, moreover, superior flexibility.     

Coupling Engineering of NH4+ Pre-Intercalation and Rich Oxygen Vacancies in Tunnel WO3 Toward Fast and Stable Rocking Chair Zinc-Ion Battery

Herein, for the first time, a pre-intercalated non-metal ion (NH₄⁺) with rich oxygen vacancies stabilized tunnel WO₃ is proposed as a new intercalation anode to construct Zn-metal-free rocking-chair ZIBs. With the ethylene glycol additive in the aqueous electrolyte, the Zn²⁺ solvation structure can be regulated and the side reaction of hydrogen evolution can also be suppressed. Owing to the integrated synergetic modification, a high-rate and ultra-stable aqueous Zn-(NH₄)_xWO₃ battery can be constructed, which exhibits an improved specific capacity (153 mAh g⁻¹ at 0.1 A g⁻¹), excellent rate performance (when the current density increases to 3 A g⁻¹, the specific capacitance is still 86 mAh g⁻¹), and a high cycle stability with 100% capacity retention after 2,200 cycles under 5 A g⁻¹. Ex situ X-ray diffraction and XPS reveal the reversible insertion/extraction of Zn²⁺ in (NH₄)_xWO₃. The assembled (NH₄)_xWO₃//MnO₂ rocking-chair ZIBs delivers excellent capacity of 82 mAh g⁻¹ at 0.1 A g⁻¹, impressive cyclic stability. Additionally, the flexible (NH₄)_xWO₃//MnO₂ ZIBs can power the electrochromic device-based PANI/WO₃ with high color contrast and fast response time. This study provides new insight for developing high-performance rechargeable aqueous ZIBs.     

Self-Supported Pd Nanorod Arrays for High-Efficient Nitrate Electroreduction to Ammonia

Electrochemical nitrate (NO₃⁻) reduction to ammonia (NH₃) offers a promising pathway to recover NO₃⁻ pollutants from industrial wastewater that can balance the nitrogen cycle and sustainable green NH₃ production. However, the efficiency of electrocatalytic NO₃⁻ reduction to NH₃ synthesis remains low for most of electrocatalysts due to complex reaction processes and severe hydrogen precipitation reaction. Herein, high performance of nitrate reduction reaction (NO₃⁻RR) is demonstrated on self-supported Pd nanorod arrays in porous nickel framework foam (Pd/NF). It provides a lot of active sites for H* adsorption and NO₃⁻ activation leading to a remarkable NH₃ yield rate of 1.52 mmol cm⁻² h⁻¹ and a Faradaic efficiency of 78% at −1.4 V versus RHE. Notably, it maintains a high NH₃ yield rate over 50 cycles in 25 h showing good stability. Remarkably, large-area Pd/NF electrode (25 cm²) shows a NH₃ yield of 174.25 mg h⁻¹, be promising candidate for large-area device for industrial application. In situ FTIR spectroscopy and density functional theory calculations analysis confirm that the enrichment effect of Pd nanorods encourages the adsorption of H species for ammonia synthesis following a hydrogenation mechanism. This work brings a useful strategy for designing NO₃⁻RR catalysts of nanorod arrays with customizable compositions.     

Hierarchical architecture of ultrashort carbon nanotubes/polyaniline nanocables coated on graphene sheets for advanced supercapacitors

Multilayer super-short carbon nanotubes (SSCNTs) could be prepared by tailoring raw multiwalled carbon nanotubes (MWCNTs) with mechanical-stirring and ultrasonic oxidation-cut method. The SSCNTs/polyaniline/reduced graphene oxide (SSCNTs/PANI/RGO) ternary hybrid composite was fabricated by reducing SSCNTs/PANI/GO precursor prepared by self-assembly from the complex dispersion of graphene oxide (GO) and the as-prepared SSCNTs/PANI nanocables, followed by redoping and reoxidation of the reduced PANI to restore the conducting structure of PANI in the ternary composite. The microscope images indicated that SSCNTs/PANI nanocables could uniformly distribute in the conductive network of graphene sheets and prevent the agglomeration of graphene. Such the hierarchical structure perfectly facilitates the contact between PANI for faradaic energy storage and electrolyte ions, and efficiently utilizes the double-layer capacitance of SSCNTs and graphene sheets at the electrode–electrolyte interfaces. The maximum specific capacitance of the SSCNTs/PANI/RGO composite achieved 845 F g^?1, which was much higher than that of pure PANI and SSCNTs/PANI nanocables. Moreover, the ternary composite also showed the good cycling stability, retaining about 96% of its initial capacitance after 1000 cycles because of the synergistic effect and conductive network of SSCNTs/PANI nanocables and graphene sheets. Therefore, the combined effects between SSCNTs/PANI nanocables and graphene sheets taking advantage of both charging and faradaic processes could readily explain the excellent electrochemical performance for supercapacitors.     

Microstructure,electrical and humidity sensing properties of TiO<Subscript>2</Subscript>/polyaniline nanocomposite films prepared by sol–gel spin coating technique

High sensitive resistive type humidity sensor based titanium oxide/polyaniline (TiO₂/PANI) nanocomposite thin films prepared by a sol–gel spin coating technique on an alumina substrate. The resultant nanocomposites were characterized by using X-ray diffraction (XRD), Field emission electron microscopy, Fourier transform infrared spectroscopy (FTIR), UV–Vis absorbance and energy dispersive spectra analysis. In the XRD patterns of both pure and TiO₂/PANI composite confirms the deposition of PANI on TiO₂ and the average size of the composite particle was found to be 32 nm. Large number of nano grain surface being covered by PANI, which agrees very well with the results obtained by XRD studies. FTIR and UV–Vis spectra reveal that the PANI component undergoes an electronic structure modification as a result of the TiO₂ and PANI interaction. The room temperature resistivity was found to be for TiO₂ and TiO₂/PANI nanocomposite films 1.42?×?10⁶ and 2.56?×?10³ Ω cm respectively. The obtained TiO₂/PANI nanocomposites sensor exhibited higher humidity sensing performance such as high sensitivity, fast response (20 s) and recovery time (15 s) and high stability.     

Scalable Synthesis of Switchable Assemblies of Gold Nanorod Lyotropic Liquid Crystal Nanocomposites

A new class of solvent free, lyotropic liquid crystal nanocomposites based on gold nanorods (AuNRs) with high nanorod content is reported. Application of shear results in switchable, highly ordered alignment of the nanorods over several centimeters with excellent storage stability for months. For the synthesis, AuNRs are surface functionalized with a charged, covalently tethered corona, which induces fluid‐like properties. This honey‐like material can be deposited on a substrate and a high orientational order parameter of 0.72 is achieved using a simple shearing protocol. Switching shearing direction results in realignment of the AuNRs. For a film containing 75 wt% of AuNRs the alignment persists for several months. In addition to the lyotropic liquid crystal characteristics, the AuNRs films also exhibit anisotropic electrical conductivity with an order of magnitude difference between the conductivities in direction parallel and perpendicular to the alignment of the AuNRs.     

Ultrahigh coulombic efficiency electrolyte enables Li||SPAN batteries with superior cycling performance

Raising the coulombic efficiency of lithium metal anode cycling is the deciding step in realizing long-life rechargeable lithium batteries. Here, we designed a highly concentrated salt/ether electrolyte diluted in a fluorinated ether: 1.8 M LiFSI in DEE/BTFE (diethyl ether/bis(2,2,2-trifluoroethyl)ether), which realized an average coulombic efficiency of 99.37% at 0.5 mA cm⁻² and 1 mAh cm⁻² for more than 900 cycles. This electrolyte also maintained a record coulombic efficiency of 98.7% at 10 mA cm⁻², indicative of its ability to provide fast-charging with high cathode loadings. Morphological studies reveal dense, dendrite free Li depositions after prolonged cycling, while surface analyses confirmed the formation of a robust LiF-rich SEI layer on the cycled Li surface. Moreover, we discovered that this ether-based electrolyte is highly compatible with the low-cost, high-capacity SPAN (Sulfurized polyacrylonitrile) cathode, where the constructed Li||SPAN cell exhibited reversible cathode capacity of 579 mAh g⁻¹ and no capacity decay after 1200 cycles. A cell where a high areal loading SPAN electrode (>3.5 mAh cm⁻²) is paired with only onefold excess Li was constructed and cycled at 1.75 mA cm⁻², maintaining a coulombic efficiency of 99.30% for the lithium metal. Computational simulations revealed that at saturation, the Li-FSI complex forms contact ion pairs, with a first solvation shell comprising DEE molecules, and a second solvation shell with a mix of DEE/BTFE. This study provides a path to enable high energy density Li||SPAN batteries with stable cycling.     

A High-Energy Asymmetric Supercapacitor Based on Tomato-Leaf-Derived Hierarchical Porous Activated Carbon and Electrochemically Deposited Polyaniline Electrodes for Battery-Free Heart-Pulse-Rate Monitoring

A simple and scalable method to fabricate a novel high-energy asymmetric supercapacitor using tomato-leaf-derived hierarchical porous activated carbon (TAC) and electrochemically deposited polyaniline (PANI) for a battery-free heart-pulse-rate monitor is reported. In this study, TAC is prepared by simple pyrolysis, exhibiting nanosheet-type morphology and a high specific surface area of ≈1440 m² g⁻¹, and PANI is electrochemically deposited onto carbon cloth. The TAC- and PANI- based asymmetric supercapacitor demonstrates an electrochemical performance superior to that of symmetric supercapacitors, delivering a high specific capacitance of 248 mF cm⁻² at a current density of 1.0 mA cm⁻². The developed asymmetric supercapacitor shows a high energy density of 270 µWh cm⁻² at a power density of 1400 µW cm⁻², as well as an excellent cyclic stability of ≈95% capacitance retention after 10 000 charging–discharging cycles while maintaining ≈98% Coulombic efficiency. Impressively, the series-connected asymmetric supercapacitors can operate a battery-free heart-pulse-rate monitor extremely efficiently upon solar-panel charging under regular laboratory illumination.     

Optimized Solid Electrolyte Interphase and Solvation Structure of Potassium Ions in Carbonate Electrolytes for High-Performance Potassium Metal Batteries

The introduction of electrolyte additives is one of the most potential strategies to improve the performance of potassium metal batteries (PMBs). However, designing an additive that can alter the K⁺ solvation shell and essentially inhibit K dendrite remains a challenge. Herein, the amyl-triphenyl-phosphonium bromide was introduced as an additive to build a stable solid electrolyte interphase layer. The amyl-TPP cations can form a cation shielding layer on the metal surface during the nucleation stage, preventing K⁺ from gathering at the tip to form K dendrites. Besides, the cations can be preferentially reduced to form K_xP_y with fast K⁺ transport kinetics. The Br⁻ anions, as Lewis bases with strong electronegativity, can not only coordinate the Lewis acid pentafluoride to inhibit the formation of HF, but also change the K⁺ solvation structure to reduce solvent molecules in the first solvation structure. Therefore, the symmetrical battery exhibits a low deposition overpotential of 123 mV at 0.1 mA cm⁻² over 4200 h cycle life. The full battery, paried with a perylene-tetracarboxylic dianhydride (PTCDA) cathode, possesses a cycle life of 250 cycles at 2 C and 81.9% capacity retention. This work offers a reasonable electrolyte design to obtain PMBs with long-term stablity and safety.